Herbicidal mixtures exhibiting a synergistics effect

ABSTRACT

The present invention relates to moulding compositions which are treated with phosphazenes and are based on polycarbonate and graft polymers chosen from the group consisting of silicone rubbers, EP(D)M rubbers and acrylate rubbers as the graft base, and which have an excellent flameproofing and very good mechanical properties, such as resistance to stress cracking or notched impact strength.

The present invention relates to moulding compositions which are treatedwith phosphazenes and are based on polycarbonate and graft polymerschosen from the group consisting of silicone rubbers, EP(D)M rubbers andacrylate rubbers as the graft base, and which have an excellentflameproofing and very good mechanical properties, such as resistance tostress cracking or notched impact strength.

DE-A 196 16 968 describes polymerizable phosphazene derivatives,processes for their preparation and their use as curable binders forpaints, coatings, fillers, stopping compositions, adhesives, mouldingsor films.

WO 97/400 92 describes flameproofed moulding compositions ofthermoplastic polymers and unsubstituted phosphazenes (PN_(n−x)H_(1−y)type).

EP-A 728 811 describes a thermoplastic mixture comprising aromaticpolycarbonate, graft copolymer based on dienes, copolymer andphosphazenes which has good flameproofing properties, impact strengthand heat distortion resistance.

The object of the present invention is to provide polycarbonate mouldingcompositions with an excellent flame resistance and excellent mechanicalproperties, such as notched impact strength and stability to stresscracking. This spectrum of properties is required in particular for usesin the field of data technology, such as, for example, for housings formonitors, printers, copiers and the like.

It has now been found that moulding compositions which are based onpolycarbonate and graft polymers chosen from the group consisting ofsilicone rubbers, EP(D)M rubbers and acrylate rubbers and comprisephosphazenes have the desired properties.

The invention therefore provides thermoplastic moulding compositionscomprising

A) polycarbonate and/or polyester-carbonate,

B) at least one rubber-elastic graft polymer chosen from the groupconsisting of silicone rubbers, EP(D)M rubbers and acrylate rubbers asthe graft base,

C) at least one thermoplastic polymer chosen from the group consistingof vinyl (co)polymers and polyalkylene terephthalates and

D) at least one phosphazene chosen from the group consisting ofphosphazene of the formulae

 wherein

R is in each case identical or different and represents amino, C₁- toC₈-alkyl or C₁- to C₈-alkoxy, in each case optionally halogenated,preferably halogenated by fluorine, or C₅- to C₆-cycloalkyl, C₆- toC₂₀-aryl, preferably phenyl or naphthyl, C₆- to C₂₀-aryloxy, preferablyphenoxy or naphthyloxy, or C₇- to C₁₂-aralkyl, preferablyphenyl-C₁-C₄-alkyl, in each case optionally substituted by alkyl,preferably C₁-C₄-alkyl, and/or halogen, preferably chlorine and/orbromine,

k represents 0 or a number from 1 to 15, preferably a number from 1 to10.

The invention preferably provides thermoplastic moulding compositionscomprising

A) 40 to 99, preferably 60 to 98.5 parts by wt. of aromaticpolycarbonate and/or polyester-carbonate

B) 0.5 to 60, preferably 1 to 40, in particular 2 to 25 parts by wt. ofat least one rubber-elastic graft polymer chosen from the groupconsisting of silicone rubbers, EP(D)M rubbers and acrylate rubbers asthe graft base,

C) 0 to 45, preferably 0 to 30, particularly preferably 2 to 25 parts bywt. of at least one thermoplastic polymer chosen from the groupconsisting of vinyl (co)polymers and polyalkylene terephthalates,

D) 0.1 to 50, preferably 2 to 35, in particular 5 to 25 parts by wt. ofat least one component chosen from the group consisting of phosphazenesof the formulae

 wherein

R is in each case identical or different and represents amino, C₁- toC₈-alkyl or C₁ to C₈-alkoxy, in each case optionally halogenated,preferably halogenated by fluorine, or C₅- to C₆-cycloalkyl, C₆- toC₂₀-aryl, preferably phenyl or naphthyl, C₆- to C₂₀-aryloxy, preferablyphenoxy or naphthyloxy, or C₇- to C₁₂-aralkyl, preferablyphenyl-C₁-C₄-alkyl, in each case optionally substituted by alkyl,preferably C₁-C₄-alkyl, and/or halogen, preferably chlorine and/orbromine,

k represents 0 or a number from 1 to 15, preferably a number from 1 to10.

E) 0 to 5, preferably 0.1 to 1, particularly preferably 0.1 to 0.5 partsby wt. of fluorinated polyolefin.

Component A

Aromatic polycarbonates and/or aromatic polyester-carbonates accordingto component A which are suitable according to the invention are knownfrom the literature or can be prepared by processes known from theliterature (for the preparation of aromatic polycarbonates see, forexample, Schnell, “Chemistry and Physics of Polycarbonates”,Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877,DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610 and DE-OS 3 832 396;for the preparation of aromatic polyester-carbonates e.g. DE-OS 3 077934).

Aromatic polycarbonates are prepared e.g. by reaction of diphenols withcarbonic acid halides, preferably phosgene, and/or with aromaticdicarboxylic acid dihalides, preferably benzenedicarboxylic aciddihalides, by the phase boundary process, optionally using chainstoppers, for example monophenols, and optionally using trifunctional ormore than trifunctional branching agents, for example triphenols ortetraphenols.

Diphenols for the preparation of the aromatic polycarbonates and/oraromatic polyester-carbonates are preferably those of the formula (III)

wherein

A is a single bond, C₁-C₅-alkylene, C₂-C₅-alkylidene,C₅-C₆-cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO₂—, C₆-C₁₂-arylene, towhich further aromatic rings optionally containing heteroatoms can befused,

or a radical of the formula (IV) or (V)

B in each case is C₁-C₁₂-alkyl, preferably methyl, or halogen,preferably chlorine and/or bromine,

x in each case independently of one another is 0, 1 or 2,

p is 1 or 0, and

R⁷ and R⁸ can be chosen individually for each X¹ and independently ofone another denote hydrogen or C₁-C₆-alkly, preferably hydrogen, methylor ethyl,

X¹ denotes carbon and

m denotes an integer from 4 to 7, preferably 4 or 5, with the provisothat on at least one atom X¹, R⁷ and R⁸ are simultaneously alkyl.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols,bis-(hydroxyphenyl)-C_(1-C) ₅-alkanes,bis-(hydroxyphenyl)-C₅-C₆-cycloalkanes, bis-(hydroxyphenyl) ethers,bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl) ketones,bis-(hydroxyphenyl) sulfones andα,α-bis-(hydroxyphenyl)-diisopropyl-benzenes, and derivatives thereofbrominated on the nucleus and/or chlorinated on the nucleus.

Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, bisphenolA, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone and di-and tetrabrominated or -chlorinated derivatives thereof, such as, forexample, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane,2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.

2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularlypreferred.

The diphenols can be employed individually or as any desired mixtures.

The diphenols are known from the literature or are obtainable byprocesses known from the literature.

Chain stoppers which are suitable for the preparation of thethermoplastic aromatic polycarbonates are, for example, phenol,p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and alsolong-chain alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenolaccording to DE-OS 2 842 005, or monoalkylphenols or dialkylphenolshaving a total of 8 to 20 C atoms in the alkyl substituents, such as3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol,p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and4-(3,5-dimethylheptyl)-phenol. The amount of chain stoppers to beemployed is in general between 0.5 mole % and 10 mole %, based on thesum of the moles of the particular diphenols employed.

The thermoplastic aromatic polycarbonates have average weight-averagemolecular weights (M_(w), measured e.g. by ultracentrifuge or scatteredlight measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.

The thermoplastic aromatic polycarbonates can be branched in a knownmanner, and in particular preferably by the incorporation of 0.05 to 2.0mole %, based on the sum of the diphenols employed, of trifunctional ormore than trifunctional compounds, for example those having three ormore phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. For thepreparation of copolycarbonates according to the invention according tocomponent A, it is also possible to employ 1 to 25 wt. %, preferably 2.5to 25 wt. % (based on the total amount of diphenols to be employed) ofpolydiorganosiloxanes with hydroxy-aryloxy end groups. These are known(see, for example, U.S. Pat. No. 3,419,634) or can be prepared byprocesses known from the literature. The preparation ofpolydiorganosiloxane-containing copolycarbonates is described e.g. inDE-OS 3 334 782.

Preferred polycarbonates are, in addition to the bisphenol Ahomopolycarbonates, the copolycarbonates of bisphenol A with up to 15mole %, based on the sum of the moles of diphenols, of other diphenolsmentioned as preferred or particularly preferred, in particular2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.

Aromatic dicarboxylic acid dihalides for the preparation of aromaticpolyester-carbonates are preferably the di-acid dichlorides ofisophthalic acid, terephthalic acid, diphenyl ether-4,4′-dicarboxylicacid and naphthalene-2,6-dicarboxylic acid.

Mixtures of the di-acid dichlorides of isophthalic acid and terephthalicacid in a ratio of between 1:20 and 20:1 are particularly preferred.

A carbonic acid halide, preferably phosgene, is additionally co-used asa bifunctional acid derivative in the preparation ofpolyester-carbonates.

Possible chain stoppers for the preparation of the aromaticpolyester-carbonates are, in addition to the monophenols alreadymentioned, also chlorocarbonic acid esters thereof, as well as the acidchlorides of aromatic monocarboxylic acids, which can optionally besubstituted by C₁-C₂₂-alkyl groups or by halogen atoms, and aliphaticC₂-C₂₂-monocarboxylic acid chlorides.

The amount of chain stoppers is in each case 0.1 to 10 mole %, based onthe moles of diphenols in the case of the phenolic chain stoppers and onthe moles of dicarboxylic acid dichlorides in the case of monocarboxylicacid chloride chain stoppers.

The aromatic polyester-carbonates can also contain incorporated aromatichydroxycarboxylic acids.

The aromatic polyester-carbonates can be both linear and branched in aknown manner (in this context see also DE-OS 2 940 024 and DE-OS 3 007934).

Branching agents which can be used are, for example, trifunctional ormore than trifunctional carboxylic acid chlorides, such as trimesic acidtrichloride, cyanuric acid trichloride,3,3′,4,4′-benzophenone-tetracarboxylic acid tetrachloride,1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromelliticacid tetrachloride, in amounts of 0.01 to 1.0 mole % (based on thedicarboxylic acid dichlorides employed), or trifunctional or more thantrifunctional phenols, such as phloroglucinol,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene,4,4-dimethyl-2,4,6-tri-(4-hydroxy-phenyl)-heptane,1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenylmethane,2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol,tetra-(4-hydroxyphenyl)-methane,2,6-bis-(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol,2-(4-hydroxy-phenyl)-2-(2,4-dihydroxyphenyl)-propane,tetra-(4-[4-hydroxy-phenylisopropyl]-phenoxy)-methane or1,4-bis-[4,4′-dihydroxytriphenyl)-methyl]-benzene, in amounts of 0.01 to1.0 mole %, based on the diphenols employed. Phenolic branching agentscan be initially introduced into the reaction vessel together with thediphenols, and acid chloride branching agents can be introduced togetherwith the acid dichlorides.

The content of carbonate structural units in the thermoplastic aromaticpolyester-carbonates can be varied as desired. The content of carbonategroups is preferably up to 100 mole %, in particular up to 80 mole %,particularly preferably up to 50 mole %, based on the sum of estergroups and carbonate groups. Both the ester and the carbonate content ofthe aromatic polyester-carbonates can be present in the polycondensatein the form of blocks or in random distribution.

The relative solution viscosity (η_(rel)) of the aromatic polycarbonatesand polyester-carbonates is in the range of 1.18 to 1.4, preferably 1.22to 1.3 (measured on solutions of 0.5 g polycarbonate orpolyester-carbonate in 100 ml methylene chloride solution at 25° C.).

The thermoplastic aromatic polycarbonates and polyester-carbonates canbe employed by themselves or in any desired mixture with one another.

Component B

Component B comprises one or more rubber-elastic graft polymers chosenfrom the group consisting of silicone rubbers, acrylate rubbers andEP(D)M rubbers as the graft base.

Component B preferably comprises one or more graft polymers of

B.1 5 to 95, preferably 20 to 80, in particular 30 to 80 wt. % of atleast one vinyl monomer on

B.2 95 to 5, preferably 80 to 20, in particular 70 to 20 wt. % of one ormore graft bases having glass transition temperatures of <10° C.,preferably <0° C., particularly preferably <−20° C., chosen from thegroup consisting of silicone rubbers, acrylate rubbers and EP(D)Mrubbers.

Graft base B.2 in general has an average particle size (d₅₀ value) of0.05 to 5 μm, preferably 0.10 to 0.5 μm, particularly preferably 0.20 to0.40 μm.

Monomers B.1 are preferably mixtures of

B.1.1 50 to 99, preferably 60 to 80 parts by wt. of vinylaromaticsand/or vinylaromatics substituted on the nucleus (such as, for example,styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene) and/ormethacrylic acid (C₁-C₈)-alkyl esters (such as e.g. methyl methacrylateand ethyl methacrylate) and

B.1.2 1 to 50, preferably 40 to 20 parts by wt. of vinyl cyanides(unsaturated nitriles, such as acrylonitrile and methacrylonitrile)and/or (meth)acrylic acid (C₁-C₈)-alkyl esters (such as e.g. methylmethacrylate, n-butyl acrylate and t-butyl acrylate) and/or derivatives(such as anhydrides and imides) of unsaturated carboxylic acids (forexample maleic anhydride and N-phenyl-maleimide).

Preferred monomers B.1.1 are chosen from at least one of the monomersstyrene, α-methylstyrene and methyl methacrylate, and preferred monomersB.1.2 are chosen from at least one of the monomers acrylonitrile, maleicanhydride and methyl methacrylate.

Particularly preferred monomers are B.1.1 styrene and B.1.2acrylonitrile.

Silicone rubbers B.2 which are suitable according to the inventionconsist predominantly of structural units

wherein

R¹¹ and R¹² can be identical or different and denote C₁-C₆-alkyl orcycloalkyl or C₆-C₁₂ aryl.

Preferred silicone rubbers B.2 are in particle form with an averageparticle diameter d₅₀ of 0.09 to 1 μm, preferably 0.09 to 0.4 μm, and agel content of more than 70 wt. %, in particular 73 to 98 wt. %, and areobtainable from

1) dihalogeno-organosilanes

2) 0 to 10 mole %, based on 1), of trihalogenosilanes and

3) 0 to 3 mole %. based on 1), of tetrahalogenosilanes and

4) 0 to 0.5 mole %, based on 1), of halogenotriorganosilanes,

wherein the organic radicals in compounds 1), 2) and 4) are

α) C₁-C₆-alkyl or cyclohexyl, preferably methyl or ethyl,

β) C₆-C₁₂-aryl, preferably phenyl,

γ) C₁-C₆-alkenyl, preferably vinyl or allyl,

δ) mercapto-C₁-C₆-alkyl, preferably mercaptopropyl

with the proviso that the sum (γ+δ) is 2 to 10 mole %, based on all theorganic radicals of the compounds 1), 2) and 4), and the molar ratioγ:δ=3:1 to 1:3, preferably 2:1 to 1:2.

Preferred silicone rubbers B.2 contain as organic radicals at least 80mole % methyl groups. The end group is in general adiorganyl-hydroxyl-siloxy unit, preferably a dimethylhydroxysiloxy unit.

Preferred silanes 1) to 4) for the preparation of silicone rubbers B.2contain chlorine as the halogen substituent.

“Obtainable” means that silicone rubber B.2 does not necessarily have tobe prepared from the halogen compounds 1) to 4). Silicone rubbers B.2 ofthe same structure which have been prepared from silanes with otherhydrolysable groups, such as e.g. C₁-C₆-alkoxy groups, or from cyclicsiloxane oligomers are also intended to be included.

Silicone graft rubbers are mentioned as a particularly preferredcomponent B.2. These can be prepared, for example, by a three-stageprocess.

In the first stage, monomers such as dimethyldichlorosilane,vinylmethyldichlorosilane or dichlorosilanes with other substituents arereacted to give the cyclic oligomers (octamethylcyclotetrasiloxane ortetravinyltetramethylcyclotetrasiloxane) which can easily be purified bydistillation (cf. Chemie in unserer Zeit 4 (1987), 121-127).

In the second stage, the crosslinked silicone rubbers are obtained fromthese cyclic oligomers by ring-opening cationic polymerization with theaddition of mercaptopropylmethyldimethoxysilane.

In the third stage, the silicone rubbers obtained, which havegrafting-active vinyl and mercapto groups, are subjected to free-radicalgrafting polymerization with vinyl monomers (or mixtures).

In the second stage, preferably, mixtures of cyclic siloxane oligomerssuch as octamethylcyclotetrasiloxane andtetramethyltetravinylcyclo-tetrasiloxane are subjected to ring-openingcationic polymerization in emulsion. The silicone rubbers are obtainedin particle form as an emulsion.

The process is particularly preferably carried out in accordance withGB-PS 1 024 014 with alkylbenzenesulfonic acids, which act bothcatalytically and as an emulsifier. After the polymerization, the acidis neutralized. Instead of alkylbenzenesulfonic acids, n-alkylsulfonicacids can also be employed. It is also possible also additionally toemploy co-emulsifiers, in addition to the sulfonic acid.

Co-emulsifiers can be nonionic or anionic. Possible anionicco-emulsifiers are, in particular, salts of n-alkyl- oralkylbenzenesulfonic acids. Nonionic co-emulsifiers are polyoxyethylenederivatives of fatty alcohols and fatty acids. Examples are POE(3)-lauryl alcohol, POE (20)-oleyl alcohol, POE (7)-nonyl alcohol or POE(10)-stearyl alcohol. (The terminology POE (number) . . . alcohol meansthat as many units of ethylene oxide as correspond to the number havebeen added on to one molecule of alcohol. POE represents polyethyleneoxide. The number is an average value.)

The crosslinking- and grafting-active groups (vinyl and mercapto groups,cf. organic radicals γ and δ) can be introduced into the silicone rubberusing corresponding siloxane oligomers. Such oligomers are e.g.tetramethyltetravinylcyclotetrasiloxane orγ-mercaptopropylmethyldimethoxysiloxane or the hydrolysis productthereof.

They are added to the main oligomer, e.g. octamethylcyclotetrasiloxane,in the desired amounts in the second stage.

The incorporation of longer-chain alkyl radicals, such as e.g. ethyl,propyl or the like, or the incorporation of phenyl groups can also beachieved analogously.

An adequate crosslinking of the silicon rubber can already be achievedif the radicals γ and δ react with one another during the emulsionpolymerization, so that the addition of an external crosslinking agentmay be dispensable. However, a crosslinking silane can be added duringthe second reaction stage in order to increase the degree ofcrosslinking of the silicone rubber.

Branchings and crosslinkings can be achieved by addition of e.g.tetraethoxysilane or a silane of the formula

y-SiX₃

wherein

X is a hydrolysable group, in particular an alkoxy or halogen radical,and

y is an organic radical.

Preferred silanes y-SiX₃ are methyltrimethoxysilane andphenyltrimethoxysilane.

The gel content is determined at 25° C. in acetone (cf. DE-AS 2 521 288,col. 6, 1. 17 to 37). In the silicone rubbers according to theinvention, it is at least 70%, preferably 73 to 98 wt. %.

Grafted silicone rubbers B can be prepared by free-radical graftingpolymerization, for example analogously to DE-PS 2 421 288.

For the preparation of the grafted silicone rubber in the third stage,the grafting monomers can be subjected to free-radical graftingpolymerization in the presence of the silicone rubber, in particular at40 to 90° C. The grafting polymerization can be carried out insuspension, dispersion or emulsion. Continuous or discontinuous emulsionpolymerization is preferred. This grafting polymerization is carried outwith free-radical initiators (e.g. peroxides, azo compounds,hydroperoxides, persulfates and perphosphates) and optionally usinganionic emulsifiers, e.g. carboxonium salts, sulfonic acid salts ororganic sulfates. Graft polymers with high grafting yields, i.e. a highcontent of the grafting monomers in the polymer is bonded chemically tothe silicon rubber, are formed by this procedure. The silicone rubberhas grafting-active radicals, so that particular measures for intensivegrafting are superfluous.

The grafted silicon rubbers can be prepared by grafting polymerizationof 5 to 95 parts by wt., preferably 20 to 80 parts by wt. of a vinylmonomer or vinyl monomer mixture on to 5 to 95, preferably 20 to 80parts by wt. silicone rubber.

A particularly preferred vinyl monomer is styrene or methylmethacrylate. Suitable vinyl monomer mixtures comprise 50 to 95 parts bywt. styrene, α-methylstyrene (or other styrenes substituted by alkyl orhalogen on the nucleus) or methyl methacrylate on the one hand and 5 to50 parts by wt. acrylonitrile, methacrylonitrile, acrylic acidC₁-C₁₈-alkly ester, methacrylic acid C₁-C₁₆-alkyl ester, maleicanhydride or substituted maleimides on the other hand. Acrylic acidesters of primary or secondary aliphatic C₂-C₁₀-alcohols, preferablyn-butyl acrylate, or acrylic or methacrylic acid esters of tert-butanol,preferably t-butyl acrylate, can additionally be present in smalleramounts as further vinyl monomers. A particularly preferred monomermixture is 30 to 40 parts by wt. α-methylstyrene, 52 to 62 parts by wt.methyl methacrylate and 4 to 14 parts by wt. acrvlonitrile.

The silicone rubbers grafted in this way can be worked up in a knownmanner, e.g. by coagulation of the latices with electrolytes (salts,acids or mixtures thereof) and subsequent purification and drying.

In the preparation of the grafted silicone rubbers, in addition to theactual graft copolymers, in general free polymers or copolymers of thegrafting monomers which form the graft shell are also formed to acertain extent. In this case, the product obtained by polymerization ofthe grafting monomers in the presence of the silicone rubber, strictlyspeaking, that is to say, in general a mixture of graft copolymer andfree (co)polymer of the grafting monomers, is called grafted siliconerubber.

Acrylate-based graft polymers preferably comprise

(a) 20 to 90 wt. %, based on the graft polymer, of acrylate rubberhaving a glass transition temperature below −20° C. as the graft baseand

(b) 10 to 80 wt. %, based on the graft polymer, of at least onepolymerizable ethylenically unsaturated monomer (cf. B.1) as thegrafting monomer.

The acrylate rubbers (a) are preferably polymers of acrylic acid alkylesters, optionally with up to 40 wt. %, based on (a), of otherpolymerizable ethylenically unsaturated monomers. Preferredpolymerizable acrylic acid esters include C₁-C₈-alkyl esters, forexample methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters;halogenoalkyl esters, preferably halogeno-C₁-C₈-alkyl esters, such aschloroethyl acrylate, and mixtures of these monomers.

For the crosslinking, monomers with more than one polymerizable doublebond can be copolymerized. Preferred examples of crosslinking monomersare esters of unsaturated monocarboxylic acids having 3 to 8 C atoms andunsaturated monohydric alcohols having 3 to 12 C atoms, or saturatedpolyols having 2 to 4 OH groups and 2 to 20 C atoms, such as e.g.ethylene glycol dimethacrylate and allyl methacrylate; polyunsaturatedheterocyclic compounds, such as e.g. trivinyl and triallyl cyanurate;polyfunctional vinyl compounds, such as di- and trivinylbenzenes; andalso triallyl phosphate and diallyl phthalate.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycoldimethacrylate, diallyl phthalate and heterocyclic compounds whichcontain at least 3 ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomerstriallyl cyanurate, triallyl isocyanurate,triacryloylhexahydro-s-triazine and triallylbenzenes.

The amount of crosslinking monomers is preferably 0.02 to 5, inparticular 0.05 to 2 wt. %, based on the rubber base.

In the case of cyclic crosslinking monomers with at least 3ethylenically unsaturated groups, it is advantageous to limit the amountto less than 1 wt. % of the rubber base.

Preferred “other” polymerizable ethylenically unsaturated monomers whichcan optionally be used in addition to the acrylic acid esters for thepreparation of graft base B.2 are e.g. acrylonitrile, styrene,α-methylstyrene, acrylamides, vinyl C₁-C₆-alkyl ethers, methylmethacrylate and butadiene. Preferred acrylate rubbers as graft base B.2are emulsion polymers which have a gel content of at least 60 wt. %.

The acrylate-based polymers are generally known, can be prepared byknown processes (e.g. EP-A 244 857) or are commercially obtainableproducts.

The gel content of the graft base is determined at 25° C. in a suitablesolvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik [PolymerAnalysis] I and II, Georg Thieme-Verlag, Stuttgart 1977).

The average particle size d₅₀ is the diameter above and below which ineach case 50 wt. % of the particles lie. It can be determined by meansof ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid. Z. undZ. Polymere 250 (1972), 782-1796).

At least one ethylene- and propylene-containing copolymer or terpolymerwith only a low number of double bonds is employed as the EP(D)M graftbase (cf. EP-A 163 411, EP-A 244 857).

EP(D)M rubbers which are used are those which have a glass transitiontemperature in the range of −60 to −40° C. The rubbers have only a lownunber of double bonds, i.e. fewer than 20 double bonds per 1,000 Catoms, in particular 3 to 10 double bonds per 1,000 C atoms. Examples ofsuch rubbers are copolymers comprising ethylene-propylene, andethylene-propylene terpolymers. The latter are prepared bypolymerization of at least 30 wt. % ethylene, at least 30 wt. %propylene and 0.5 to 15 wt. % of a non-conjugated diolefinic component.Diolefins having at least 5 carbon atoms, such as5-ethylidenenorbornene, dicyclopentadiene, 2,2,1-dicyclopentadiene and1,4-hexadiene, are as a rule used as the ternary component.Polyalkenamers, such as polypentenamer, polyoctenamer, polydodecenameror mixtures of these substances, are used as a rule. Partly hydrogenatedpolybutadiene rubbers in which at least 70% of the residual double bondsare hydrogenated are furthermore also possible. Of the abovementionedrubbers, the ethylene-propylene copolymers and the ethylene-propyleneterpolymers (EPDM) rubbers are used in particular. As a rule, EPDMrubbers have a Mooney viscosity ML₁₋₄ (100° C.) of 25 to 120. They arecommercially obtainable.

The EP(D)M-based graft polymer can be prepared by various methods.Preferably, a solution of the EP(D)M elastomer (rubber) in the monomermixture and (optionally) inert solvents is prepared and the graftingreaction is carried out by free-radical initiators, such as azocompounds or peroxides, at elevated temperatures. The processes of DE-AS23 02 014 and DE-OS 25 33 991 may be mentioned as examples. It is alsopossible to carry out the reaction in suspension, as described in U.S.Pat. No. 4,202,948.

Component C

Component C comprises one or more thermoplastic vinyl (co)polymers C.1and/or polyalkylene terephthalates C.2.

Suitable vinyl (co)polymers C.1 are polymers of at least one monomerfrom the group consisting of vinylaromatics, vinyl cyanides (unsaturatednitrites), (meth)acrylic acid (C₁-C₈)-alkyl esters, unsaturatedcarboxylic acids and derivatives (such as anhydrides and imides) ofunsaturated carboxylic acids. Particularly suitable (co)polymers arethose of

C.1.1 50 to 99, preferably 60 to 80 parts by wt. of vinylaromaticsand/or vinylaromatics substituted on the nucleus (such as, for example,styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene) and/ormethacrylic acid (C₁-C₈)-alkyl esters (such as e.g. methyl methacrylateand ethyl methacrylate), and

C.1.2 1 to 50, preferably 20 to 40 parts by wt. of vinyl cyanides(unsaturated nitriles), such as acrylonitrile and methacrylonitrile,and/or (meth)acrylic acid (C₁-C₈)-alkyl esters (such as e.g. methylmethacrylate, n-butyl acrylate and t-butyl acrylate) and/or unsaturatedcarboxylic acids (such as maleic acid) and/or derivatives (such asanhydrides and imides) of unsaturated carboxylic acids (for examplemaleic anhydride and N-phenyl-maleimide).

(Co)polymers C.1.1 are resinous, thermoplastic and rubber-free.

The copolymer of C.1.1 styrene and C.1.2 acrylonitrile is particularlypreferred.

(Co)polymers according to C.1 are known and can be prepared byfree-radical polymerization, in particular by emulsion, suspension,solution or bulk polymerization. The (co)polymers preferably havemolecular weights {overscore (M)}_(w) (weight-average, determined bylight scattering or sedimentation) of between 15,000 and 200,000.(Co)polymers according to component C.1 are often formed as by-productsin the grafting polymerization of component B, especially if largeamounts of monomers B.1 are grafted on to small amounts of rubber B.2.The amount of C.1 optionally also to be employed according to theinvention does not include these by-products of the graftingpolymerization of B.

The polyalkylene terephthalates of component C.2 are reaction productsof aromatic dicarboxylic acids or their reactive derivatives, such asdimethyl esters or anhydrides, and aliphatic, cycloaliphatic oraraliphatic diols, and mixtures of these reaction products.

Preferred polyalkylene terephthalates contain at least 80 wt. %,preferably at least 90 wt. %, based on the dicarboxylic acid component,of terephthalic acid radicals and at least 80 wt. %, preferably at least90 mole %, based on the diol component, of ethylene glycol and/orbutane-1,4-diol radicals.

The preferred polyalkylene terephthalates can contain, in addition toterephthalic acid radicals, up to 20 mole %, preferably up to 10 mole %of radicals of other aromatic or cycloaliphatic dicarboxylic acidshaving 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 Catoms, such as e.g. radicals of phthalic acid, isophthalic acid,naphthalene-2,6-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid,succinic acid, adipic acid, sebacic acid, azelaic acid orcyclohexane-diacetic acid.

The preferred polyalkylene terephthalates can contain, in addition toethylene glycol or butane-1,4-diol radicals, up to 20 mole %, preferablyup to 10 mole %, of other aliphatic diols having 3 to 12 C atoms orcycloaliphatic diols having 6 to 21 C atoms, e.g. radicals ofpropane-1,3-diol, 2-ethylpropane-1,3-diol, neopentylglycol,pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol,3-ethylpentane-2,4-diol, 2-methylpentane-2,4-diol,2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1,3-diol,2,2-diethylpropane-1,3-diol, hexane-2,5-diol,1,4-di-(β-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane,2,2-bis-(4-β-hydroxyethoxy-phenyl)-propane and2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-OS 2 407 674, 2 407 776 and2 715 932).

The polyalkylene terephthalates can be branched by incorporation ofrelatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basiccarboxylic acids, e.g. in accordance with DE-OS 1 900 270 and U.S. Pat.No. 3,692,744. Examples of preferred branching agents are trimesic acid,trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Polyalkylene terephthalates which have been prepared solely fromterephthalic acid and reactive derivatives thereof (e.g. dialkyl estersthereof) and ethylene glycol and/or butane-1,4-diol, and mixtures ofthese polyalkylene terephthalates are particularly preferred.

Mixtures of polyalkylene terephthalates comprise 1 to 50 wt. %,preferably 1 to 30 wt. % polyethylene terephthalate and 50 to 99 wt. %,preferably 70 to 99 wt. % polybutylene terephthalate.

The polyalkylene terephthalates preferably used in general have alimiting viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g,measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25° C. inan Ubbelohde viscometer.

The polyalkylene terephthalates can be prepared by known methods (seee.g. Kunststoff-Handbuch [Plastics Handbook], volume VIII, p. 695 etseq., Carl-Hanser-Verlag, Munich 1973).

Component D

Phosphazenes according to component D which are employed according tothe present invention are linear phosphazenes according to formula (Ia)and cyclic phosphazenes according to formula (Ib)

wherein

k and R have the meaning given above.

Examples which may be mentioned are: propoxyphosphazene,phenoxyphosphazene, methylphenoxyphosphazene, amino-phosphazene andfluoroalkylphosphazenes.

Phenoxyphosphazene is preferred.

The phosphazenes can be employed by themselves or as a mixture. Theradical R can always be the same, or 2 or more radicals in the formulae(Ia) and (Ib) can be different.

The phosphazenes and their preparation are described, for example, inEP-A 728 811, DE-A 1 961 668 and WO 97/40092.

Component E

The fluorinated polyolefins E are of high molecular weight and haveglass transition temperatures of above −30° C., as a rule above 100° C.,fluorine contents preferably of 65 to 76, in particular 70 to 76 wt. %and average particle diameters d₅₀ of 0.05 to 1,000, preferably 0.08 to20 μm. In general, the fluorinated polyolefins F have a density of 1.2to 2.3 g/cm³. Preferred fluorinated polyolefins F arepolytetrafluoroethylene, polyvinylidene fluoride andtetrafluoroethylene/hexafluoropropylene and ethylene/tetrafluoroethylenecopolymers. The fluorinated polyolefins are known (cf. “Vinyl andRelated Polymers” by Schildknecht, John Wiley & Sons, Inc., New York,1962, page 484-494; “Fluorpolymers” [Fluoropolymers] by Wall,Wiley-Interscience, John Wiley & Sons, Inc., New York, volume 13, 1970,page 623-654; “Modern Plastics Encyclopedia”, 1970-1971, volume 47, no.10 A, October 1970, McGraw-Hill, Inc., New York, page 134 and 774;“Modern Plastics Encyclopedia”, 1975-1976, October 1975, volume 52, no.10 A, McGraw-Hill, Inc., New York, page 27, 28 and 472 and U.S. Pat.Nos. 3,671,487, 3,723,373 and 3,838,092).

They can be prepared by known processes. thus, for example, bypolymerization of tetrafluoroethylene in an aqueous medium with acatalyst which forms free radicals, for example sodium peroxydisulfate,potassium peroxydisulfate or ammonium peroxydisulfate, under pressuresof 7 to 71 kg/cm² and at temperatures of 0 to 200° C., preferably attemperatures of 20 to 100° C. (For further details see e.g. U.S. Pat.No. 2,393,967). The density of these materials can be between 1.2 and2.3 g/cm³ and the average particle size between 0.5 and 1,000 μm,depending on the use form.

Fluorinated polyolefins E which are preferred according to the inventionare tetrafluoroethylene polymers having an average particle diameter of0.05 to 20 μm, preferably 0.08 to 10 μm, and a density of 1.2 to 1.9g/cm³, and are preferably employed in the form of a coagulated mixtureof emulsions of tetrafluoroethylene polymers E with emulsions of thegraft polymers.

Suitable fluorinated polyolefins E which can be employed in powder formare tetrafluoroethylene polymers having an average particle diameter of100 to 1,000 μm and densities of 2.0 g/cm³ to 2.3 g/cm³.

To prepare a coagulated mixture of graft polymer and component E, anaqueous emulsion (latex) of a graft polymer B is first mixed with afinely divided emulsion of a tetraethylene polymer E; suitabletetrafluoroethylene polymer emulsions usually have solids contents of 30to 70 wt. %, in particular 50 to 60 wt. %, preferably 30 to 35 wt. %.

The equilibrium ratio of graft polymer to tetrafluoroethylene polymer Ein the emulsion mixture is 95:5 to 60:40. The emulsion mixture is thencoagulated in a known manner, for example by spray drying, freeze dryingor coagulation by means of addition of inorganic or organic salts, acidsor bases or organic water-miscible solvents, such as alcohols orketones, preferably at temperatures of 20 to 150° C., in particular 50to 100° C. If necessary, the product can be dried at 50 to 200° C.,preferably 70 to 100° C.

Suitable tetrafluoroethylene polymer emulsions are commerciallyconventional products and are available, for example, from DuPont asTeflon® 30 N.

The moulding compositions according to the invention can comprise atleast one of the conventional additives, such as lubricants and mouldrelease agents, nucleating agents, antistatics, stabilizers anddyestuffs and pigments.

The moulding compositions according to the invention can comprise up to35 wt. %, based on the total moulding composition, of a furtherflameproofing agent which optionally has a synergistic action. Examplesof further flameproofing agents which are mentioned are organicphosphorus compounds, such as triphenyl phosphate orm-phenylene-bis-(diphenyl phosphate), organic halogen compounds, such asdecabromobisphenyl ether and tetrabromobisphenol, inorganic halogencompounds, such as ammonium bromide, nitrogen compounds, such asmelamine and melamine-formaldehyde resins, inorganic hydroxidecompounds, such as Mg hydroxide and Al hydroxide, inorganic compoundssuch as antimony oxides, barium metaborate, hydroxoantimonate, zirconiumoxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zincborate, ammonium borate, barium metaborate, talc, silicate, siliconoxide and tin oxide, and siloxane compounds.

The moulding compositions according to the invention comprisingcomponents A to E and optionally further known additives, such asstabilizers, dyestuffs, pigments, lubricants and mould release agents,nucleating agents and antistatics, are prepared by mixing the particularconstituents in a known manner and subjecting the mixture to meltcompounding and melt extrusion at temperatures of 200° C. to 300° C. inconventional units, such as internal kneaders, extruders and twin-screwextruders, component E preferably being employed in the form of thecoagulated mixture already mentioned.

The mixing of the individual constituents can be carried out in a knownmanner both successively and simultaneously, and in particular both atabout 20° C. (room temperature) and at a higher temperature.

The invention therefore also provides a process for the preparation ofthe moulding compositions.

On the basis of their excellent flame resistance and their goodmechanical properties, the thermoplastic moulding compositions accordingto the invention are suitable for the production of all types of shapedarticles, in particular those with increased requirements of resistanceto fracture and resistance to chemicals.

The moulding compositions according to the present invention can be usedfor the production of any type of shaped articles. In particular, shapedarticles can be produced by injection moulding. Examples of shapedarticles which can be produced are: any type of housing components, e.g.for domestic appliances, such as juice presses, coffee machines andmixers, and for office machines, such as monitors, printers and copiers,covering sheets for the building sector and components for the motorvehicle sector. They can furthermore be employed in the field ofelectrical engineering, because they have very good electricalproperties.

The moulding compositions according to the invention can moreover beused, for example, for the production of the following shaped articlesor mouldings:

interior fittings for railway vehicles (FR), hub caps, housings ofelectrical equipment containing small transformers, housings forequipment for dissemination and transmission of information, housingsand lining for medical purposes, massage equipment and housingstherefor, toy vehicles for children, flat wall elements, housings forsafety equipment, rear spoilers, thermally insulated transportationcontainers, devices for housing or care of small animals, mouldings forsanitary and bath fittings, covering grids for ventilator openings,mouldings for garden and equipment buildings, housings for gardenequipment.

Another form of processing is the production of shaped articles bythermoforming from previously produced sheets or films.

The present invention therefore also provides the use of the mouldingcompositions according to the invention for the production of all typesof shaped articles, preferably those mentioned above, and the shapedarticles produced from the moulding compositions according to theinvention.

EXAMPLES Component A

Linear polycarbonate based on bisphenol A with a relative solutionviscosity of 1.26, measured in CH₂Cl₂ as the solvent at 25° C. and aconcentration of 0.5 g/100 ml.

Component B

B.1 Silicone Graft Rubber

1. Preparation of the Silicone Rubber Emulsion

38.4 parts by wt. octamethylcyclotetrasiloxane, 1.2 parts by wt.tetramethyltetravinylcyclotetrasiloxane and 1 part by wt.Mercaptopropyl-methyldimethoxysilane are stirred with one another. 0.5part by wt. dodecylbenzenesulfonic acid is added, and 58.4 parts by wt.water are then added in the course of one hour. During this procedurethe mixture is stirred intensively. The pre-emulsion is homogenizedtwice with the aid of a high-pressure emulsifying machine under 200 bar.A further 0.5 part by wt. dodecylbenzenesulfonic acid is added. Theemulsion is stirred for 2 hours at 85° C. and then for 36 hours at 20°C. It is neutralized with the aid of 5N NaOH. A stable emulsion with asolids content of approx. 36 wt. % results. The polymer has a gelcontent of 82 wt. %, measured in toluene; the average particle diameterd₅₀ is 300 nm.

2. Preparation of the Grafted Silicone Rubber

The following are initially introduced into a reactor:

2,107 parts by wt. latex according to 1) and

1,073 parts by wt. water.

After initiation with a solution of 7.5 parts by wt. potassiumperoxydisulfate in 195 parts by wt. water at 65° C., in each case thefollowing solutions are fed in uniformly in the course of 4 hours forpreparation of the graft rubber:

Solution 1:

540 parts by wt. styrene and

210 parts by wt. acrylonitrile;

Solution 2:

375 parts by wt. water and

15 parts by wt. of the sodium salt of C₁₄-C₁₈-alkylsulfonic acids

The polymerization is then in each case brought to completion in thecourse of 6 hours at 65° C. A latex with a solids content of approx. 33wt. % results.

After coagulation with an aqueous magnesium chloride/acetic acidsolution, filtration and drying in vacuo, the graft polymers areobtained in the form of white powders.

B.2 Acrylate Graft Rubber

Graft polymer of 40 parts by wt. of a copolymer of styrene andacrylonitrile in a ratio of 72:28 on 60 parts by wt. crosslinkedpolyacrylate rubber in particle form (average particle diameter d₅₀=0.5μm) prepared by emulsion polymerization.

B.3 EPDM Graft Rubber

Graft polymer of 50 parts by wt. of a copolymer of styrene andacrylonitrile in a ratio of 72:28 on 50 parts by wt. crosslinked EPDMrubber from Uniroyal Chemical Company, tradename Royaltuf 372 P29.

B.4

Graft polymer of 45 parts by wt. of a copolymer of styrene andacrylonitrile in a ratio of 72:28 on 55 parts by wt. crosslinkedpolybutadiene rubber in particle form (average particle diameterd₅₀=0.40 μm) prepared by emulsion polymerization.

Component C

Styrene/acrylonitrile copolymer with a styrene/acrylonitrile weightratio of 72:28 and a limiting viscosity of 0.55 dl/g (measurement indimethylformamide at 20° C.).

Component D

Phenoxyphosphazene of the formula

Commercial product P-3800 from Nippon Soda Co., Ltd., Japan.

Component E

Tetrafluoroethylene polymer as a coagulated mixture of an SAN graftpolymer emulsion (SAN graft polymer of 40 parts by wt. of a copolymer ofstyrene and acrylonitrile in a ratio of 73:27 on 60 parts by wt. ofcrosslinked polybutadiene rubber in particle form (average particlediameter d₅₀=0.28 μm) prepared by emulsion polymerization) in water anda tetrafluoroethylene polymer emulsion in water. The weight ratio ofgraft polymer to tetrafluoroethylene polymer E in the mixture is 90 wt.% to 10 wt. %. The tetrafluoroethylene polymer emulsion has a solidscontent of 60 wt. % and the average particle diameter is between 0.05and 0.5 μm. The SAN graft polymer emulsion has a solids content of 34wt. % and an average latex particle diameter of d₅₀=0.28 μm.

Preparation of E

The emulsion of the tetrafluoroethylene polymer (Teflon 30 N fromDuPont) is mixed with the emulsion of the SAN graft polymer and themixture is stabilized with 1.8 wt. %, based on the polymer solids, ofphenolic antioxidants. The mixture is coagulated with an aqueoussolution of MgSO₄ (Epsom salt) and acetic acid at pH 4 to 5 at 85 to 95°C. and filtered and the residue is washed until practically free fromelectrolytes, subsequently freed from most of the water bycentrifugation and thereafter dried to a powder at 100° C. This powdercan then be compounded with the further components in the unitsdescribed.

Preparation and Testing of the Moulding Compositions According to theInvention

The components are mixed on a 3 lnternal kneader. The shaped articlesare produced on an injection moulding machine type Arburg 270 E at 260°C.

The Vicat B heat distortion point is determined in accordance with DIN53 460 (ISO 306) on bars of dimensions 80×10×4 mm.

The stress cracking properties (ESC properties) were investigated onbars of dimensions 80×10×4 mm, processing temperature 260° C. A mixtureof 60 vol. % toluene and 40 vol. % isopropanol was used as the testmedium. The test specimens were pre-elongated by means of a circular arctemplate (pre-elongation in per cent) and kept in the test medium atroom temperature. The stress cracking properties were evaluated from thecracking and fracture as a function of the pre-elongation in the testmedium.

TABLE Moulding compositions and their properties 4 1 2 3 ComparisonComponents (parts by wt.) A 66.7 66.7 66.7 66.7 B.1 7.3 — — — B.2 — 7.3— — B.3 — — 7.3 — B.4 — — — 7.3 C 9.4 9.4 9.4 9.4 D 12.0 12.0 12.0 12.0E 4.2 4.2 4.2 4.2 Mould release agent 0.4 0.4 0.4 0.4 Properties 61 6164 51 ak (ISO 180/1 A) (kJ/m²) Vicat B120 (ISO 306) (° C.) 107 107 108103 ESC properties 7:30 5:50 9:10 4:20 fracture at el. = 2.4% (min:sec)UL 94V 1.6 mm V-0 V-0 V-0 V-0

The moulding compositions according to the invention are distinguishedby a favourable combination of properties of flameproofing andmechanical properties. Surprisingly, the notched impact strength and ESCproperties, which can be regarded as a measure of the resistance tochemicals, are improved decisively by the altered rubber bases comparedwith the prior art (diene rubber). In the resistance to stress cracking,the moulding compositions according to the invention withstand fracturefor considerably longer, which can be decisive for critical uses(components of complicated geometries).

What is claimed is:
 1. A thermoplastic molding composition comprising A)at least one resin selected from the group consisting of polycarbonateand polyester-carbonate, B) at least one rubber-elastic graft polymerhaving a graft base selected from the group consisting of siliconerubber, EP(D)M rubber and acrylate rubber, C) at least one thermoplasticpolymer selected from the group consisting of vinyl (co)polymer andpolyalkylene terephthalate and D) at least one phosphazene selected fromthe group consisting of phosphazenes of the formulae

 wherein R is in each case identical or different and represents anamino group, C₁- to C₈-alkyl, C₁- to C₈-alkoxy, C₅-C₆-cycloalkyl,C₆-C₂₀-aryl, C₆-C₂₀-aryloxy or C₇-C₂-aralkyl, in each case optionallysubstituted by alkyl and/or halogen, and k represents 0 or a number from1 to
 15. 2. Moulding compositions according to claim 1, comprising 40-99parts by wt. component A, 0.5-60 parts by wt. component B, 0-45 parts bywt. component C, 0.1-50 parts by wt. component D and 0.05-5 parts by wt.fluorinated polyolefin.
 3. Moulding compositions according to claim 1,comprising at least one additive chosen from the group consisting oflubricants and mould release agents, nucleating agents, antistatics,stabilisers, dyestuffs and pigments.
 4. Moulding compositions accordingto claim 1, comprising a flameproofing agent which differs fromcomponent D.
 5. Process for the preparation of moulding compositionsaccording to claim 1, wherein components A to E and optionally additivesare mixed and the mixture is subjected to melt compounding.
 6. Themolding composition of claim 1 wherein B) is a graft polymers of B.1 5to 95 wt. % of at least one vinyl monomer on B.2 95 to 5 wt. % of one ormore graft bases having a glass transition temperature of <10° C. 7.Molding compositions according to claim 6, wherein B.1 is derived fromB.1.1 50 to 99 parts by wt. of a vinylaromatic monomer and/ormethacrylic acid (C₁-C₈)-alkyl esters and B.1.2 1 to 50 parts by wt. ofat least one member selected from the group consisting of vinyl cyanide,(meth)acrylic acid (C₁-C₈)-alkyl ester and derivatives of unsaturatedcarboxylic acid.”
 8. The molding composition according to claim 7,wherein B.1.1 is a member selected from the group consisting of styrene,α-methylstyrene and methyl methacrylate and B.1.2 is a member selectedfrom the group consisting of acrylonitrile, maleic anhydride and methylmethacrylate.
 9. The molding composition according to claim 1, whereincomponent C.1 is a vinyl (co)polymer of at least one monomer from thegroup consisting of vinylaromatic, vinyl cyanide, (meth)acrylic acid(C₁-C₈)-alkyl ester, unsaturated carboxylic acid and derivative ofunsaturated carboxylic acid.
 10. A method of using the composition ofclaim 1 comprising producing a shaped article.
 11. A shaped articleprepared by the method of claim 10.